US4375576A - Enhanced diisobutene production in the presence of methyl tertiary butyl ether - Google Patents
Enhanced diisobutene production in the presence of methyl tertiary butyl ether Download PDFInfo
- Publication number
- US4375576A US4375576A US06/287,193 US28719381A US4375576A US 4375576 A US4375576 A US 4375576A US 28719381 A US28719381 A US 28719381A US 4375576 A US4375576 A US 4375576A
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- United States
- Prior art keywords
- isobutene
- mtbe
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- mole
- diisobutene
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 239000000539 dimer Substances 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 2
- 229940023913 cation exchange resins Drugs 0.000 abstract 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 125000000542 sulfonic acid group Chemical group 0.000 description 7
- 238000006384 oligomerization reaction Methods 0.000 description 6
- 238000006471 dimerization reaction Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- -1 i.e. Chemical compound 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- ZCKODQRJCONMMC-UHFFFAOYSA-N 1-[2,3-bis(ethenyl)phenoxy]-2,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(OC=2C(=C(C=C)C=CC=2)C=C)=C1C=C ZCKODQRJCONMMC-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- KXYDGGNWZUHESZ-UHFFFAOYSA-N 4-(2,2,4-trimethyl-3h-chromen-4-yl)phenol Chemical compound C12=CC=CC=C2OC(C)(C)CC1(C)C1=CC=C(O)C=C1 KXYDGGNWZUHESZ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001447 polyvinyl benzene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/177—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by selective oligomerisation or polymerisation of at least one compound of the mixture
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
Definitions
- the present invention relates to the separation of isoolefins from streams containing mixtures of an isoolefin and the corresponding normal olefin.
- the present invention is especially useful for the separation of isobutene from streams containing n-butenes by oligomerizing the isobutene. More particularly, the present invention results in a higher diisobutene production and less of the higher oligomers or polymers.
- Isoolefins of four carbon atoms are difficult to separate from the corresponding normal olefin by simple fractionation because of the closeness of their boiling points.
- the isoolefin is selectively absorbed by sulfuric acid and the resulting isoolefin-containing sulfuric acid extract is then diluted and heated or treated with steam to separate the isoolefin.
- Isobutene and diisobutene are of significant value having diverse applications, for example, isobutene is one of the comonomers for butyl rubber and diisobutene is an intermediate in the preparation of detergents.
- the isobutene oligomers are useful as polymer gasoline.
- the n-butenes are required in pure form for homopolymerization and as feeds for the oxidative production of butadiene.
- One manner of separating these components is to pass the mixture through what is called a cold acid extraction procedure wherein the stream is fed into a bath of concentrated sulfuric acid.
- U.S. Pat. No. 4,215,011 disclosed the use of acid cation exchange resin in a heterogenous combination reaction-distillation system for the selective dimerization of isobutene in the presence of normal butenes. Although some codimer between n-butenes and isobutene are formed, the reaction is highly preferential for the reaction of isobutene with itself and provides a means to separate isobutene from a C 4 stream with little loss of other normal butenes.
- the present process is suited to treat other isoolefin-normal olefins mixtures, it is of particular significance for the recovery of product streams with sufficiently low levels of isobutene to be processable to obtain useable n-butenes and particularly butene-1 which is the n-butene isomer employed in homopolymerization to produce polybutene or copolymerization with other monomers and as the preferred feed for oxidative dehydrogenation to produce butadiene-1,3.
- the present process relates to fixed bed liquid phase systems wherein the isobutene is removed from a feed stream and a oligomer product of the isobutene recovered.
- the oligomerization is not easily controlled and in addition to diisobutene higher oligomers are produced, some of which form deposits on the resin catalyst reducing its effectiveness. Furthermore, the production of higher oligomers reduces the amount of the desired diisobutene.
- the diisobutene is preferred, since it is used for alkylations and is also useful as a gasoline blending stock, whereas the other lower oligomers, i.e., trimers and tetramers are not used for the alkylation and are no better as gasoline blending stock than the dimer.
- enhancement and suppression are obtained by the addition of a small amount of a relatively non-contaminating material to the reaction system.
- Another feature of the present process is the substantial energy saving over the cold acid method of isobutene removal.
- the present invention is the discovery that the inclusion of a small amount of methyl tertiary butyl ether (MTBE) in a feed containing isobutene and other C 4 , particularly n-butenes to a reactor containing a fixed bed cation ion exchange resin for reacting the isobutene to form oligomers in a liquid phase process for separating the isobutene from the other components of the feeds, enhances the dimerization of isobutene while suppressing the further reaction of isobutene to form higher oligomers or polymers.
- MTBE methyl tertiary butyl ether
- the resultant product stream contains the isobutene dimers oligomers product, unreacted C 4 's and some MTBE.
- This stream is normally fractionated, e.g., by distillation to recover the unreacted C 4 's as an overhead fraction and the oligomer and MTBE as a bottoms. If the presence of MTBE is not desired in the oligomer fraction, a further distillation may be carried out or the first distillation may be carried out with an intermediate draw stream in the distillation column to recover a stream high in MTBE and containing some oligomer which can be recycled to the oligomerization reaction.
- the oligomer reaction is exothermic and means to control the temperature in the catalyst bed are provided such as heat exchange means or the dilution of the feed stream with inerts.
- the reaction may be cooled too effectively by the other components of the feed stream and, it may actually be necessary to add heat to the reaction via the heat exchangers or by preheating the feed.
- the preferred temperature of the reaction in the catalyst bed is in the range of 35° to 160° C., preferably 100° C.
- the higher temperatures favor the reaction of isobutene, and under normal conditions favor the oligomerization as well as side reactions such as copolymerization of n-butenes with the isobutene, however, the MTBE also tends to suppress the oligomerization (polymerization beyond the dimer) and the side reactions also.
- the mechanism by which the advantageous result of the present invention is obtained, is not known. That is, whether the MTBE, effects the catalyst to moderate its activity or enters into some reaction to stop the secondary oligomerizations is not known. It is fortuitous that the MTBE is detrimental only to the undesirable secondary oligomerization, whereby the dimerization of isobutene is actually enhanced.
- oligomer is used herein to mean lower polymers of isobutene having greater than eight carbon atoms.
- the feed to the catalyst bed in the reactor may comprise up to 100 percent of the hydrocarbon feed to the reactor generally 5 to 100 mole % isobutene however, usually there will be other components of such a stream such as butene-1, butene-2, normal butane and isobutene, and the isobutene will comprise from about 9 to 60 mole % of the stream. Small amounts generally less than 1 mole % of the total stream may be C 3 and C 5 hydrocarbon, although now a refinery C 4 cut will be able to exclude the lower and higher hydrocarbons.
- the amount of MTBE is small, usually an amount of at least 0.001 mole and no more than 1 mole per mole of isobutene in the feed stream to obtain the desired result. However, it is preferred that an amount in the range of 0.005 to 0.05 mole MTBE per mole of isobutene be used.
- the residence time of the feed in the catalyst bed in conjunction with the temperature may be adjusted to maximize the isobutene removal or dimerization with the range of 0.1 to 10.0 liquid hourly space velocity (LHSV) which means the liquid volumes of hydrocarbon per volume of reactor containing catalyst per hour.
- LHSV liquid hourly space velocity
- the LHSV will be in the range of 0.5 to 4.0, which would represent a moderately sized reactor with good unit productivity. It is appreciated that shorter residences times represent the feed throughput. Although it may be most advantageous to have small or moderate sized units, and high throughput, it would not be unreasonable to have a very large reactor with a low LHSV to obtain a feasible throughput.
- the pressure employed in the reactor is that sufficient to maintain the liquid phase under the temperature condition employed, which will generally be from about 16 to 25 atmospheres.
- Catalysts suitable for the present process are cation exchangers, which contain sulfonic acid groups, and which have been obtained by polymerization or copolymerization of aromatic vinyl compounds followed by sulfonation.
- aromatic vinyl compounds suitable for preparing polymers or copolymers are: Styrene, vinyl toluene, vinyl naphthalene, vinyl ethylbenzene, methyl styrene, vinyl chlorobenzene and vinyl xylene.
- a large variety of methods may be used for preparing these polymers; for example, polymerization alone or in admixture with other monovinyl compounds.
- polyvinyl compounds for example, with divinyl benzene, divinyl toluene, divinylphenylether and others.
- the polymers may be prepared in the presence of absence of solvents or dispersing agents, and various polymerization initiators may be used, e.g., inorganic or organic peroxides, persulfates, etc.
- the sulfonic acid group may be introduced into these vinyl aromatic polymers by various known methods; for example, by sulfating the polymers with concentrated sulfuric acid or chlorosulfonic acid, or by copolymerizing aromatic compounds which contain sulfonic acid groups (see e.g., U.S. Pat. No. 2,366,007). Further sulfonic acid groups may be introduced into these polymers which already contain sulfonic acid groups; for example, by treatment with fuming sulfuric acid, i.e., sulfuric acid which contains sulfur trioxide. The treatment with fuming sulfuric acid is preferably carried out at 0° to 150° C., and the sulfuric acid should contain sufficient sulfur trioxide after the reaction.
- the resulting products preferably contain an average of 1.3 to 1.8 sulfonic acid groups per aromatic nucleus.
- suitable polymers which contain sulfonic acid groups are copolymers of aromatic monovinyl compounds with aromatic polyvinyl compounds, particularly divinyl compounds, in which the polyvinyl benzene content is preferably 1 to 20% by weight of the copolymer (see, for example, German Patent Specification No. 908,247).
- the ion exchange resin is preferably used in a granular size of about 0.25 to 1 mm, although particles from 0.15 mm up to about 1 mm may be employed.
- the finer catalysts provide high surface area, but also result in high pressure drops through the reactor.
- the macroreticular form of these catalysts is preferred because of the much larger surface area exposed and the limited swelling which all of these resins undergo in a non-aqueous hydrocarbon medium.
- acid resins are suitable, such as perfluorosulfonic acid resins which are copolymers of sulfonyl fluorovinyl ethyl and fluorocarbon and described in greater detail in DuPont "Innovation", Volume 4, No. 3, Spring 1973 or the modified forms thereof as described in U.S. Pat. Nos. 3,784,399; 3,770,567 and 3,849,243.
- the catalyst may be packed into the reactor in bulk, in tubes or in the catalyst structures described in U.S. Pat. No. 4,215,011.
- the reactor may be horizontal, inclined or vertical.
- the fractionation of the product stream is entirely conventional, including the recovery and recycle of a part of the product stream to the reaction.
- the reactor 10 is a vertical stainless steel tubular reactor with the resin catalyst bed 11 supported through the middle portion.
- the hydrocarbon product is removed via line 12.
- the stream 12 is split and a portion 13 is sent for storage or processing to recover isobutene dimer and unreacted isobutene for recycle (not shown) to line 18 which is the isobutene feed.
- a portion of the hydrocarbon product from line 12 passes via 15 for recycle to mix with incoming isobutene feed 18.
- This stream 15 contains dimer, unreacted isobutene and some MTBE (also other by-products).
- the isobutene feed 18 passes through a heat exchange 19 where its temperature is adjusted usually by heating and hence, into the recycle line 15. (Note the heating of feed 18 and cooling of recycle 15 may be carried out as the same step by direct or indirect contacting of the two).
- Make up MTBE is added via 20 to the combined streams 18 and 15.
- the three streams fresh feed, and recycle
- the recycle stream is pumped by pump 14 into recycle line 15 which passes through heat exchanger recycle line 15 which passes through heat exchanger 16 where it is cooled (note above).
- the heat exchanger 16 may be used to heat the recycle.
- Other items of standard equipment are not shown, but would be employed as obviously desirable or necessary, e.g., safety valves, liquid level indicators, drains, vents, etc.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
Claims (13)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US06/287,193 US4375576A (en) | 1981-07-27 | 1981-07-27 | Enhanced diisobutene production in the presence of methyl tertiary butyl ether |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/287,193 US4375576A (en) | 1981-07-27 | 1981-07-27 | Enhanced diisobutene production in the presence of methyl tertiary butyl ether |
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US4375576A true US4375576A (en) | 1983-03-01 |
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US06/287,193 Expired - Lifetime US4375576A (en) | 1981-07-27 | 1981-07-27 | Enhanced diisobutene production in the presence of methyl tertiary butyl ether |
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Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4540839A (en) * | 1984-03-26 | 1985-09-10 | Petro-Tex Chemical Corporation | Process for the production of polymer gasoline |
US4571439A (en) * | 1985-07-22 | 1986-02-18 | Tenneco Oil Company | Method for controlled oligomerization/etherification of propylene |
US4579990A (en) * | 1985-07-15 | 1986-04-01 | Tenneco Oil Company | Process for the oligomerization of propylene |
US5118871A (en) * | 1988-11-22 | 1992-06-02 | Exxon Chemical Patents Inc | Minimizing deactivation of ether synthesis catalyst |
US5149892A (en) * | 1991-10-22 | 1992-09-22 | Ppg Industries, Inc. | Chlorinated benzenes |
US5714640A (en) * | 1994-01-21 | 1998-02-03 | Mobil Oil Corporation | Vapor pocket reactor |
US20030050522A1 (en) * | 2001-09-05 | 2003-03-13 | Fortum Oyj | Method for product separation and purification in iso-butylene dimerization process |
US20030088134A1 (en) * | 2001-07-26 | 2003-05-08 | Veli-Matti Purola | Fuel components and their selective manufacturing methods |
US6596913B1 (en) | 2001-02-23 | 2003-07-22 | Catalytic Distillation Technologies | Recovery of tertiary butyl alcohol |
US6613108B1 (en) | 1998-10-16 | 2003-09-02 | Fortum Oil & Gas Oy | Process for producing a fuel component |
US20040006252A1 (en) * | 2002-03-15 | 2004-01-08 | Catalytic Distillation Technologies | Production of diisobutene from tertiary butyl alcohol |
US20040097773A1 (en) * | 2002-08-06 | 2004-05-20 | Oxeno Olefinchemie Gmbh | Oligomerization of isobutene in N-butenic hydrocarbon streams |
WO2004080935A1 (en) | 2003-03-10 | 2004-09-23 | Fortum Oyj | Process for dimerizing light olefins |
US20050049448A1 (en) * | 2003-07-25 | 2005-03-03 | Loescher Mitchell E. | Oligomerization process |
US20050113612A1 (en) * | 1999-05-04 | 2005-05-26 | Catalytic Distillation Technologies | Process for the production of gasoline stocks |
US20070161843A1 (en) * | 2001-08-21 | 2007-07-12 | Catalytic Distillation Technologies | Pulse flow reaction |
US20070191662A1 (en) * | 2005-10-28 | 2007-08-16 | Neste Oil Oyj | Process for dimerizing olefins |
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